Carboxanilides, their preparation and compositions containing them for controlling harmful fungi

ABSTRACT

Carboxanilides of the formula I  where the substituents have the following meanings: 
     R is substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy or phenyl; 
     A is one of the radicals A1 to A5 ##STR1## where R 1  is hydrogen or alkyl; 
     R 2  is halogen or alkyl; 
     R 3  is alkyl or haloalkyl; 
     n is 1 or 2, 
     methods of manufacturing them, and agents containing them and their use for controlling harmful fungi.

The present invention relates to carboxanilides of the formula I##STR2## where the substituents have the following meanings: R

is C₃ -C₁₂ -alkyl, C₂ -C₁₂ -alkoxy, C₃ -C₁₂ -alkenyl, C₃ -C₁₂-alkenyloxy, C₃ -C₆ -alkynyl, C₃ -C₆ -alkynyloxy, where these groups canbe partially or completely halogenated;

C₃ -C₇ -cycloalkyl, C₄ -C₇ -cycloalkenyl, C₃ -C₇ -cycloalkyloxy or C₄-C₇ -cycloalkenyloxy, where these rings can carry one to three C₁ -C₄-alkyls;

phenyl, which can carry one to five halogens and/or one to three of thefollowing radicals: C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁-C₄ -haloalkoxy, C₁ -C₄ -alkylthio or C₁ -C₄ -haloalkylthio;

A is a cyclic radical from the group consisting of the formulae A1 toA5: ##STR3## where the substituents have the following meanings: R¹ ishydrogen or C₁ -C₄ -alkyl;

R² is halogen or C₁ -C₄ -alkyl;

R³ is C₁ -C₄ -alkyl or C₁ -C₄ -haloalkyl;

n is 1 or 2, where the radicals R¹ can be different if the value of n is2,

where R is not phenyl if A is 3-methylthien-2-yl, excluding compounds Iwhere A is A5 and

R³ is methyl if R is cyclopentyl, cyclohexyl or cycloheptyl or where

R³ is difluoromethyl if R is cyclohexyl, 4-t-butylcyclohexyl,cyclohexyloxy, cyclohex-1-en-1-yl, 2,6-dimethylcyclohex-1-en-1-yl,4-ethylcyclohex-1-en-1-yl, 4-t-butylcyclohex-1-en-1-yl, cyclopentyl,1-methylcyclopentyl, 1-methylcyclopentoxy,5,5-dimethylcyclopent-1-en-1-yl, 4-methylcyclopent-1-en-1-yl,cycloheptyl or cyclohept-1-en-1-yl or where

R³ is chlorodifluoromethyl if R is cyclopentyl or cycloheptyl or where

R³ is trifluoromethyl if R is cyclohexyl, 3-methylcyclohexyl,4-t-butylcyclohexyl, cyclohexyloxy, 4-methylcyclohexyloxy,2,6-dimethylcyclohexyloxy, cyclohex-1-en-1-yl,4-ethylcyclohex-1-en-1-yl, 2-isopropylcyclohex-1-en-1-yl,6-isopropylcyclohex-1-en-1-yl, 4-t-butylcyclohex-1-en-1-yl,6-ethyl-2-methylcyclohex-1-en-1-yl, 6-isopropylcyclohex-1-en-1-yl,cyclopentyl, 1-methylcyclopentyl, 1-methylcyclopentoxy,2-methylcyclopent-1-en-1-yl, 3-methylcyclopent-1-en-1-yl,4-methylcyclopent-1-en-1-yl, cycloheptyl or cyclohept-1-en-1-yl.

The invention additionally relates to the preparation of thesecompounds, compositions containing them and their use for controllingharmful fungi, in particular Botrytis.

N-(2-Methylphenyl)-3-methylthiophene-2-carboxamide,N-(2-methylphenyl)-2,5-dimethylthiophene-3-carboxamide andN-(2-methylphenyl)-1,3,5-trimethylpyrazole-4-carboxamide are known fromthe literature as fungicidal active compounds (DE-A 2 701 091; Pestic.Biochem. Physiol., 25 (2), (1986) 188-204).

The subsequently published application WO-A 93/11,117 additionallydescribes the pyrazolecarboxanilides excluded from the compounds I asbeing fungicidally active.

It is an object of the present invention to provide novel fungicidallyactive compounds having an improved spectrum of action.

We have found that this object is achieved by the compounds I defined atthe beginning.

We have additionally found processes for preparing these compounds,compositions containing them and their use for controlling harmfulfungi.

The compounds I are in general obtained by reacting a carboxylic acidhalide of the formula II in a manner known per se (e.g. J. March,Advanced Organic Chemistry, 2nd Ed., 1977, 382 ff., McGraw-Hill) with ananiline of the formula III in the presence of a base. ##STR4##

The radical Hal in the formula II is a halogen such as chlorine, bromineor iodine, in particular chlorine or bromine. This reaction iscustomarily carried out at temperatures from -20° C. to 100° C.,preferably 0° C. to 50° C.

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane,cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene,o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane,chloroform and chlorobenzene, ethers such as diethyl ether, diisopropylether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone and tert-butyl methylketone, alcohols such as methanol, ethanol, n-propanol, isopropanol,n-butanol and tert-butanol, and also dimethyl sulfoxide anddimethylformamide, particularly preferably toluene and tetrahydrofuran.

Mixtures of the solvents mentioned can also be used.

Suitable bases are generally inorganic compounds such as alkali metaland alkaline earth metal hydroxides such as lithium hydroxide, sodiumhydroxide, potassium hydroxide and calcium hydroxide, alkali metal andalkaline earth metal oxides such as lithium oxide, sodium oxide, calciumoxide and magnesium oxide, alkali metal and alkaline earth metalhydrides such as lithium hydride, sodium hydride, potassium hydride andcalcium hydride, alkali metal amides such as lithium amide, sodium amideand potassium amide, alkali metal and alkaline earth metal carbonatessuch as lithium carbonate and calcium carbonate and also alkali metalhydrogencarbonates such as sodium hydrogencarbonate, and organometalliccompounds, in particular alkali metal alkyls such as methyllithium,butyllithium and phenyllithium, alkylmagnesium halides such asmethylmagnesium chloride and also alkali metal and alkaline earth metalalkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide,potassium tert-butoxide and dimethoxymagnesium, additionally organicbases, e.g. tertiary amines such as trimethylamine, triethylamine,tri-isopropylethylamine and N-methylpiperidine, pyridine, substitutedpyridines such as collidine, lutidine and 4-dimethylaminopyridine andalso bicyclic amines.

Triethylamine and pyridine are particularly preferably used.

The bases are in general employed in equimolar amounts based on thecompound II. However, they can also be used in an excess of from 5 mol %to 30 mol %, preferably 5 mol % to 10 mol %, or--in the case of the useof tertiary amines--if appropriate as a solvent.

The starting materials are in general reacted with one another inequimolar amounts. It may be advantageous for the yield to employ II inan excess of from 1 mol % to 20 mol %, preferably 1 mol % to 10 mol %,based on III.

The starting substances of the formulae II and III needed for preparingthe compounds I are known or can be synthesized analogously to the knowncompounds (Helv. Chim. Acta, 60, (1977) 978; Zh. Org. Khim., 26, (1990)1527; Heterocycles 26, (1987) 1885; Izv. Akad. Nauk. SSSR Ser. Khim.,(1982) 2160; THL 28 593 (1987); THL 29, (1988) 5463).

Compounds I in which A is a 2-aminothiazole A4 are obtained particularlyadvantageously by first preparing the correspondingN-phenyl-2-halothiazole-5-carboxanilide V from a2-halothiazole-5-carboxylic acid halide of the formula IV and an anilineof the formula III and then reacting V with ammonia to give thecorresponding carboxanilide I.4. ##STR5##

Hal¹ and Hal² are in each case halogens such as chlorine, bromine andiodine, chlorine being preferred in the position Hal¹ and chlorine andbromine being preferred in the position Hal².

The reaction of V with ammonia is carried out in a manner known per seat from 50° C. to 200° C., at from 1 to 200 atm., preferably 5 to 50atm., in an inert solvent in the presence of a catalyst.

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane,cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene,o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane,chloroform and chlorobenzene, ethers such as diethyl ether, diisopropylether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran,nitriles such as acetonitrile and propionitrile, ketones such asacetone, methyl ethyl ketone, diethyl ketone and tert-butyl methylketone, alcohols such as methanol, ethanol, n-propanol, isopropanol,n-butanol and tert-butanol and also dimethyl sulfoxide anddimethylformamide, particularly preferably alcohols such as ethanol andisopropanol.

Mixtures of the solvents mentioned can also be used.

Suitable catalysts are, for example, phenylsulfonic acid andhydroxybenzoic acid.

The catalyst is in general employed in amounts of from 0.1 mol % to 20mol %, preferably from 0.5 mol % to 5 mol % based on V.

With respect to their use in fungicidal compositions, suitable compoundsof the formula I are those in which the substituents have the followingmeanings:

R

is C₂ -C₁₂ -alkyl such as ethyl and straight-chain or branched propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl,particularly straight-chain or branched C₃ -C₁₀ -alkyl such as propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl,n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl,1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethylbutyl, 2-ethylbutyl, 1-ethyl-3-methylpropyl, n-heptyl,1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl,1-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl,1-propylpentyl, 2-propylpentyl, nonyl, 1-methyloctyl, 2-methyloctyl,1-ethylheptyl, 2-ethylheptyl, 1-propylhexyl, 2-propylhexyl, decyl,1-methylnonyl, 2-methylnonyl, 1-ethyloctyl, 2-ethyloctyl, 1-propylheptyland 2-propylheptyl, in particular propyl, 1-methylethyl, butyl,1-methylbutyl, 2-methylbutyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl,hexyl, heptyl and 1-methylheptyl, where these groups can be partially orcompletely halogenated, ie. the hydrogens of these groups can bepartially or completely replaced by halogens such as fluorine, chlorineand bromine, in particular fluorine and chlorine, for example haloalkylsuch as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

C₂ -C₁₂ -alkoxy such as ethoxy and straight-chain or branched propoxy,butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy,undecyloxy and dodecyloxy, particularly straight-chain or branched C₂-C₁₀ -alkoxy such as ethoxy, propoxy, 1-methylethoxy, butoxy,1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy,1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,2-dimethylpropoxy,1-ethylpropoxy, n-hexyloxy, 1-methylpentoxy, 2-methylpentoxy,3-methylpentoxy, 4-methylpentoxy, 1,2-dimethylbutoxy,1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 1,2-dimethylbutoxy,2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 1,1,2-trimethylpropoxy,1,2,2-trimethylpropoxy, 1-ethylbutoxy, 2-ethylbutoxy,1-ethyl-2-methylpropoxy, n-heptyloxy, 1-methylhexyloxy,2-methylhexyloxy, 3-methylhexyloxy, 4-methylhexyloxy, 5-methylhexyloxy,1-ethylpentoxy, 2-ethylpentoxy, 1-propylbutoxy, octyloxy,1-methylheptyloxy, 2-methylheptyloxy, 1-ethylhexyloxy, 2-ethylhexyloxy,1-propylpentoxy, 2-propylpentoxy, nonyloxy, 1-methyloctyloxy,2-methyloctyloxy, 1-ethylheptyloxy, 2-ethylheptyloxy, 1-propylhexyloxy,2-propylhexyloxy, decyloxy, 1-methylnonyloxy, 2-methylnonyloxy,1-ethyloctyloxy, 2-ethyloctyloxy, 1-propylheptyloxy and2-propylheptyloxy, in particular ethoxy, propoxy, 1-methylethoxy,butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy,hexyloxy and 2-ethylhexyloxy, where these groups can be partially orcompletely halogenated, ie. the hydrogens of these groups can bepartially or completely replaced by halogens such as fluorine, chlorineand bromine, in particular fluorine and chlorine, for example haloalkoxysuch as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy,difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy,dichlorofluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy,2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy,2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy,2,2-di-chloro-2-fluoroethoxy, 2,2,2-trichloroethoxy andpentafluoroethoxy;

C₃ -C₁₂ -alkenyl such as straight-chain or branched propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl anddodecenyl, particularly straight-chain or branched C₃ -C₁₀ -alkenyl suchas 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl -2-propenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 1-methyl-2-hexenyl,2-methyl-2-hexenyl, 1-methyl-3-hexenyl, 2-methyl-3-hexenyl,1-ethyl-2-pentenyl, 2-ethyl-2-pentenyl, 1-ethyl-3-pentenyl,2-ethyl-3-pentenyl, 1-methyl-2-heptenyl, 2-methyl-2-heptenyl,1-methyl-3-heptenyl, 2-methyl-3-heptenyl, 1-ethyl-2-hexenyl,2-ethyl-2-hexenyl, 1-ethyl-3-hexenyl, 2-ethyl-3-hexenyl,1-methyl-2-octenyl, 2-methyl-2-octenyl, 1-methyl-3-octenyl,2-methyl-3-octenyl, 1-ethyl-2-heptenyl, 2-ethyl-2-heptenyl,1-ethyl-3-heptenyl, 2-ethyl-3-heptenyl, 1-ethyl-2-octenyl,2-ethyl-2-octenyl, 1-ethyl-3-octenyl and 2-ethyl-3-octenyl, inparticular 1-propenyl, 2-propenyl, 1-methylethenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 1-ethyl-2-propenyl, 1-methyl-2-butenyl,1-ethyl-2-butenyl, 1-(1-methylethyl)-2-butenyl, 1-butyl-2-butenyl,1-methyl-2-pentenyl and 1,4-dimethyl-2-pentenyl, where these groups canbe partially or completely halogenated, ie. the hydrogens of thesegroups can be partially or completely replaced by halogens such asfluorine, chlorine and bromine, in particular fluorine and chlorine, inparticular 3-chloro-2-propenyl, 2,3-dichloro-2-propenyl,2,3,3-trichloro-2-propenyl;

C₃ -C₁₂ -alkenyloxy such as straight-chain or branched propenyloxy,butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy,nonenyloxy, decenyloxy, undecenyloxy and dodecenyloxy, particularlystraight-chain or branched C₃ -C₁₀ -alkenyloxy such as 2-propenyloxy,2-butenyloxy, 3-butenyloxy, 1-methyl-2-propenyloxy,2-methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy,1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy,1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy,1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy,1-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy,5-hexenyloxy, 1-methyl-2-pentenyloxy, 2-methyl-2-pentenyloxy,3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy,2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy,1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy,4-methyl-4-pentenyloxy, 1,1-dimethyl-2-butenyloxy,1,1-dimethyl-3-butenyloxy, 1,2-dimethyl-2-butenyloxy,1,2-dimethyl-3-butenyloxy, 1,3-dimethyl-2-butenyloxy,1,3-dimethyl-3-butenyloxy, 2,2-dimethyl-3-butenyloxy,2,3-dimethyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy,1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy, 2-ethyl-2-butenyloxy,2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy,1-ethyl-1-methyl-2-propenyloxy, 1-ethyl-2-methyl-2-propenyloxy,1-methyl-2-pentenyloxy, 2-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy,2-methyl- 3-pentenyloxy, 1-methyl-2-hexenyloxy, 2-methyl-2-hexenyloxy,1-methyl-3-hexenyloxy, 2-methyl-3-hexenyloxy, 1-ethyl-2-pentenyloxy,2-ethyl-2-pentenyloxy, 1-ethyl-3-pentenyloxy, 2-ethyl-3-pentenyloxy,1-methyl-2-heptenyloxy, 2-methyl-2-heptenyloxy, 1-methyl-3-heptenyloxy,2-methyl-3-heptenyloxy, 1-ethyl-2-hexenyloxy, 2-ethyl-2-hexenyloxy,1-ethyl-3-hexenyloxy, 2-ethyl-3-hexenyloxy, 1-methyl-2-octenyloxy,2-methyl-2-octenyloxy, 1-methyl-3-octenyloxy, 2-methyl-3-octenyloxy,1-ethyl-2-heptenyloxy, 2-ethyl-2-heptenyloxy, 1-ethyl-3-heptenyloxy,2-ethyl-3-heptenyloxy, 1-ethyl-2-octenyloxy, 2-ethyl-2-octenyloxy,1-ethyl-3-octenyloxy and 2-ethyl-3-octenyloxy, in particular2-propenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy,2-pentenyloxy, 3-pentenyloxy, 1-methyl-2-butenyloxy and1-methyl-2-pentenyloxy, where these groups can be partially orcompletely halogenated, ie. the hydrogens of these groups can bepartially or completely replaced by halogens such as fluorine, chlorineand bromine, in particular fluorine and chlorine, in particular3-chloro-2-propenyloxy, 2,3-dichloro-2-propenyloxy and2,3,3-trichloro-2-propenyloxy;

C₃ -C₆ -alkynyl such as 2-propynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl,4-alkynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and1-ethyl-1-methyl-2-propynyl, in particular 2-propynyl, 2-butynyl and3-butynyl, where these groups can be partially or completelyhalogenated, ie. the hydrogens of these groups can be partially orcompletely replaced by halogens such as fluorine, chlorine and bromine,in particular fluorine and chlorine, for example 3-chloro-2-propynyl,3-chloro-2-butynyl and 4-chloro-3-butynyl;

C₃ -C₆ -alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy,1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 3-pentynyloxy,4-pentynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy,1-methyl-2-butynyloxy, 1,1-dimethyl-2-propionyloxy,1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-alkynyloxy,5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy,1-methyl-4-pentynyloxy, 2-methyl-3-pentynyloxy, 2-methyl-4-pentynyloxy,3-methyl-4-pentynyloxy, 4-methyl-3-pentynyloxy,1,1-dimethyl-2-butynyloxy, 1,1-dimethyl-3-butynyloxy,1,2-dimethyl-3-butynyloxy, 2,2-dimethyl-3-butynyloxy,1-ethyl-2-butynyloxy, 1-ethyl-3-butynyloxy, 2-ethyl-3-butynyloxy and1-ethyl-1-methyl-2-propynyloxy, preferably 2-propynyloxy, 2-butynyloxy,1-methyl-2-propynyloxy and 1-methyl-2-butynyloxy, 2-propynyloxy,2-butynyloxy, 3-butynyloxy and 1-methyl-2-propynyloxy, where thesegroups can be partially or completely halogenated, ie. the hydrogens ofthese groups can be partially or completely replaced by halogens such asfluorine, chlorine and bromine, in particular fluorine and chlorine, forexample 3-chloro-2-propynyloxy, 3-chloro-2-butynyloxy and4-chloro-3-butynyloxy;

C₃ -C₇ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl, where these rings can carry one to three C₁-C₄ -alkyls such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

C₄ -C₇ -cycloalkenyl such as cyclobutenyl, cyclopentenyl, cyclohexenyland cycloheptenyl, where these rings can carry one to three C₁ -C₄-alkyls such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

C₃ -C₇ -cycloalkoxy such as cyclopropoxy, cyclobutoxy, cyclopentoxy,cyclohexyloxy and cycloheptyloxy, where these rings can carry one tothree C₁ -C₄ -alkyls such as methyl, ethyl, propyl, 1-methylethyl,butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

or C₄ -C₇ -cycloalkenyloxy such as 1-cyclobutenyloxy, 2-cyclobutenyloxy,1-cyclopentenyloxy, 2-cyclopentenyloxy, 3-cyclopentenyloxy,1-cyclohexenyloxy, 2-cyclohexenyloxy, 3-cyclohexenyloxy,1-cycloheptenyloxy, 2-cycloheptenyloxy, 3-cycloheptenyloxy and4-cycloheptenyloxy, where these rings can carry one to three C₁ -C₄-alkyls such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

phenyl, which can carry one to five halogens such as fluorine, chlorine,bromine and iodine, in particular fluorine, chlorine and bromine, and/orone to three of the following radicals:

C₁ -C₄ -alkyl as mentioned above;

C₁ -C₄ -haloalkyl as mentioned above;

C₁ -C₄ -alkoxy as mentioned above;

C₁ -C₄ -haloalkoxy as mentioned above;

C₁ -C₄ -alkylthio such as methylthio, ethylthio, propylthio,1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and1,1-dimethylethylthio;

or C₁ -C₄ -haloalkylthio, particularly C₁ -C₂ -haloalkylthio such aschloromethylthio, dichloromethylthio, trichloromethylthio,fluoromethylthio, difluoromethylthio, trifluoromethylthio,chlorofluoromethylthio, dichlorofluoromethylthio,chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio,2,2-difluoroethylthio, 2,2,2-trifluoroethylthio,2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio,2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio andpentafluoroethylthio.

A

is a cyclic radical from the group consisting of the formulae A1 to A5:##STR6## where the substituents have the following meanings: R¹ ishydrogen or C₁ -C₄ -alkyl as mentioned above;

R² is halogen as mentioned above or C₁ -C₄ -alkyl as mentioned above;

R³ is C₁ -C₄ -alkyl as mentioned above or C₁ -C₄ -haloalkyl as mentionedabove;

n is 1 or 2, where the radicals R¹ can be different if the value of n is2,

where R is not phenyl if A is 3-methylthien-2-yl, excluding compounds Iwhere A is A5 and

R³ is methyl if R is cyclopentyl, cyclohexyl or cycloheptyl or where

R³ is difluoromethyl if R is cyclohexyl, 4-t-butylcyclohexyl,cyclohexyloxy, cyclohex-1-en-1-yl, 2,6-dimethylcyclohex-1-en-1-yl,4-ethylcyclohex-1-en-1-yl, 4-t-butylcyclohex-1-en-1-yl, cyclopentyl,1-methylcyclopentyl, 1-methylcyclopentoxy,5,5-dimethylcyclopent-1-en-1-yl, 4-methylcyclopent-1-en-1-yl,cycloheptyl or cyclohept-1-en-1-yl or where

R³ is chlorodifluoromethyl if R is cyclopentyl or cycloheptyl or where

R³ is trifluoromethyl if

R

is cyclohexyl, 3-methylcyclohexyl, 4-t-butylcyclohexyl, cyclohexyloxy,4-methylcyclohexyloxy, 2,6-dimethylcyclohexyloxy, cyclohex-1-en-1-yl,4-ethylcyclohex-1-en-1-yl, 2-isopropylcyclohex-1-en-1-yl,6-isopropylcyclohex-1-en-1-yl, 4-t-butylcyclohex-1-en-1-yl,6-ethyl-2-methylcyclohex-1-en-1-yl, 6-isopropylcyclohex-1-en-1-yl,cyclopentyl, 1-methylcyclopentyl, 1-methylcyclopentoxy,2-methylcyclopent-1-en-1-yl, 3-methylcyclopent-1-en-1-yl,4-methylcyclopent-1-en-1-yl, cycloheptyl or cyclohept-1-en-1-yl.

With respect to the biological action, particularly preferred compoundsof the formula I are those in which R has the abovementioned meaningsand A is a cyclic radical from the group consisting of the formulae A1to A5, in which the substituents are the following radicals:

R¹ is hydrogen or methyl;

R² is halogen such as fluorine, chlorine and bromine or methyl

R³ is methyl or C₁ -haloalkyl such as chloromethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl and chlorodifluoromethyl;

n is 1 or 2, where the radicals R¹ can be different if the value of n is2,

where R is not phenyl if A is 3-methylthien-2-yl.

Those compounds of the formula I are particularly preferred in which Rhas the abovementioned meaning and A is a cyclic radical from the groupconsisting of the formulae A1 to A5, in which the substituents are thefollowing groups:

R¹ is hydrogen or methyl;

R² is chlorine or methyl;

R³ is methyl, difluoromethyl or trifluoromethyl;

n is 1 or 2, where the radicals R¹ can be different if the value of n is2,

where R is not phenyl if A is 3-methylthien-2-yl.

Particularly preferred compounds of the formula I are additionally:

Compounds I in which

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopentyl, cyclohexyl,cyclopent-2-en-1-yl, phenyl or 1,1,2,2-tetrafluoroethoxy.

Compounds I in which

A is A1, A3, A4 or A5, preferably compounds I in which

A is A1, A3, A4 or A5 and

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopentyl, cyclohexyl,cyclopent-2-en-1-yl, phenyl or 1,1,2,2-tetrafluoroethoxy and

in particular compounds I in which

A is A1, A3, A4 or A5 and

R is isobutyl, sec-butyl, cyclopentyl, cyclohexyl or phenyl.

Compounds I in which

A is A1,

preferably compounds I in which

A is A1 and

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopentyl, cyclohexyl,cyclopent-2-en-1-yl, phenyl or 1,1,2,2-tetrafluoroethoxy and

in particular compounds I in which

A is A1 and

R is isobutyl, sec-butyl, cyclopentyl, cyclohexyl or phenyl.

Compounds I in which

A is A3 and

R² is chlorine or methyl,

preferably compounds I in which

A is A3,

R² is chlorine or methyl and

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopentyl, cyclohexyl,cyclopent-2-en-1-yl, phenyl or 1,1,2,2-tetrafluoroethoxy,

in particular compounds I in which

A is A3,

R² is chlorine or methyl and

R is isobutyl, sec-butyl, cyclopentyl, cyclohexyl, cyclopent-2-en-1-ylor phenyl.

Compounds I in which

A is A4 and

R³ is methyl or trifluoromethyl,

preferably compounds I in which

A is A4,

R³ is methyl or trifluoromethyl and

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopentyl, cyclohexyl,cyclopent-2-en-1-yl, phenyl or 1,1,2,2-tetrafluoroethoxy and

in particular compounds I in which

A is A4,

R³ is methyl or trifluoromethyl and

R is isobutyl, sec-butyl, cyclopentyl, cyclohexyl or phenyl.

Compounds I in which

A is A5 and

R³ is methyl or trifluoromethyl,

preferably compounds I in which

A is A5,

R³ is methyl or trifluoromethyl and

R is isobutyl, sec-butyl, 2-ethylbutyl, cyclopent-2-en-1-yl, phenyl or1,1,2,2-tetrafluoroethoxy and

in particular compounds I in which

A is A5,

R³ is methyl or trifluoromethyl and

R is isobutyl, sec-butyl, 2-ethylbutyl or 1,1,2,2-tetrafluoroethoxy.

Particularly preferred compounds of the formula I are summarized in thefollowing Tables A to E.

                  TABLE A                                                         ______________________________________                                         ##STR7##                      I.1                                                    R                                                                     ______________________________________                                                i-C.sub.3 H.sub.7                                                             n-C.sub.3 H.sub.7                                                             n-C.sub.4 H.sub.9                                                             sec.-C.sub.4 H.sub.9                                                          i-C.sub.4 H.sub.9                                                             tert.-C.sub.4 H.sub.9                                                         n-C.sub.5 H.sub.11                                                            sec-C.sub.5 H.sub.11                                                          n-C.sub.6 H.sub.13                                                            n-C.sub.7 H.sub.15                                                            sec.-C.sub.7 H.sub.15                                                         1-Methylvinyl                                                                 2-Methylvinyl                                                                 Allyl                                                                         2-Methylallyl                                                                 2-Ethylallyl                                                                  1-Methylallyl                                                                 l-Ethylallyl                                                                  1-Methyl-2-butenyl                                                            l-Ethyl-2-butenyl                                                             1-Isopropyl-2-butenyl                                                         1-n-Butyl-2-butenyl                                                           1-Methyl-2-pentenyl                                                           1,4-Dimethyl-2-pentenyl                                                       Propargyl                                                                     2-Butynyl                                                                     3-Butynyl                                                                     Ethoxy                                                                        Propoxy                                                                       1-Methylethoxy                                                                n-Butoxy                                                                      1-Methylpropoxy                                                               2-Methylpropoxy                                                               1,1-Dimethylethoxy                                                            n-Pentyloxy                                                                   n-Hexyloxy                                                                    2-Ethylhexyloxy                                                               2-Propenyloxy                                                                 2-Butenyloxy                                                                  2-Methyl-2-propenyloxy                                                        2-Pentenyloxy                                                                 3-Pentenyloxy                                                                 3-Chloro-2-propenyloxy                                                        2,3-Dichloro-2-propenyloxy                                                    2,3,3-Trichloropropenyloxy                                                    2-Propynyloxy                                                                 2-Butynyl-oxy                                                                 3-Butynyl-oxy                                                                 1-Methyl-2-propynyloxy                                                        Cyclopropyl                                                                   Cyclobutyl                                                                    Cyclopentyl                                                                   Cyclohexyl                                                                    3-Cyclopentenyl                                                               1-Cyclopentenyl                                                               3-Cyclohexenyl                                                                1-Cyclohexenyl                                                                Cyclopentyloxy                                                                Cyclohexyloxy                                                                 3-Cyclopentenyloxy                                                            3-Cyclohexenyloxy                                                             Phenyl                                                                        2-Fluorophenyl                                                        ______________________________________                                    

                  TABLE B                                                         ______________________________________                                         ##STR8##                      I.2                                            (R.sup.1).sub.n   R                                                           ______________________________________                                        5-CH.sub.3        i-C.sub.3 H.sub.7                                           5-CH.sub.3        n-C.sub.3 H.sub.7                                           5-CH.sub.3        n-C.sub.4 H.sub.9                                           5-CH.sub.3        sec.-C.sub.4 H.sub.9                                        5-CH.sub.3        i-C.sub.4 H.sub.9                                           5-CH.sub.3        tert.-C.sub.4 H.sub.9                                       5-CH.sub.3        n-C.sub.5 H.sub.11                                          5-CH.sub.3        sec-C.sub.5 H.sub.11                                        5-CH.sub.3        n-C.sub.6 H.sub.13                                          5-CH.sub.3        n-C.sub.7 H.sub.15                                          5-CH.sub.3        sec.-C.sub.7 H.sub.15                                       5-CH.sub.3        Ethoxy                                                      5-CH.sub.3        Propoxy                                                     5-CH.sub.3        1-Methylethoxy                                              5-CH.sub.3        n-Butoxy                                                    5-CH.sub.3        1-Methylpropoxy                                             5-CH.sub.3        2-Methylpropoxy                                             5-CH.sub.3        1,1-Dimethylethoxy                                          5-CH.sub.3        n-Pentyloxy                                                 5-CH.sub.3        n-Hexyloxy                                                  5-CH.sub.3        Cyclopentyl                                                 5-CH.sub.3        Cyclohexyl                                                  5-CH.sub.3        3-Cyclopentenyl                                             5-CH.sub.3        1-Cyclopentenyl                                             5-CH.sub.3        3-Cyclohexenyl                                              5-CH.sub.3        1-Cyclohexenyl                                              5-CH.sub.3        Cyclopentyloxy                                              5-CH.sub.3        Cyclohexyloxy                                               5-CH.sub.3        2-Cyclopentenyloxy                                          4,5-(CH.sub.3).sub.2                                                                            i-C.sub.3 H.sub.7                                           4,5-(CH.sub.3).sub.2                                                                            n-C.sub.3 H.sub.7                                           4,5-(CH.sub.3).sub.2                                                                            n-C.sub.4 H.sub.9                                           4,5-(CH.sub.3).sub.2                                                                            sec.-C.sub.4 H.sub.9                                        4,5-(CH.sub.3).sub.2                                                                            i-C.sub.4 H.sub.9                                           4,5-(CH.sub.3).sub.2                                                                            tert.-C.sub.4 H.sub.9                                       4,5-(CH.sub.3).sub.2                                                                            n-C.sub.5 H.sub.11                                          4,5-(CH.sub.3).sub.2                                                                            sec-C.sub.5 H.sub.11                                        4,5-(CH.sub.3).sub.2                                                                            n-C.sub.6 H.sub.13                                          4,5-(CH.sub.3).sub.2                                                                            n-C.sub.7 H.sub.15                                          4,5-(CH.sub.3).sub.2                                                                            sec.-C.sub.7 H.sub.15                                       4,5-(CH.sub.3).sub.2                                                                            Ethoxy                                                      4,5-(CH.sub.3).sub.2                                                                            Propoxy                                                     4,5-(CH.sub.3).sub.2                                                                            1-Methylethoxy                                              4,5-(CH.sub.3).sub.2                                                                            n-Butoxy                                                    4,5-(CH.sub.3).sub.2                                                                            1-Methylpropoxy                                             4,5-(CH.sub.3).sub.2                                                                            2-Methylpropoxy                                             4,5-(CH.sub.3).sub.2                                                                            1,1-Dimethylethoxy                                          4,5-(CH.sub.3).sub.2                                                                            n-Pentyloxy                                                 4,5-(CH.sub.3).sub.2                                                                            n-Hexyloxy                                                  4,5-(CH.sub.3).sub.2                                                                            Cyclopentyl                                                 ______________________________________                                    

                  TABLE C                                                         ______________________________________                                         ##STR9##                      I.3                                            R.sup.a   R.sup.b  R.sup.2  R                                                 ______________________________________                                        H         H        Cl       i-C.sub.3 H.sub.7                                 H         H        Cl       n-C.sub.3 H.sub.7                                 H         H        Cl       n-C.sub.4 H.sub.9                                 H         H        Cl       sec.-C.sub.4 H.sub.9                              H         H        Cl       i-C.sub.4 H.sub.9                                 H         H        Cl       tert.-C.sub.4 H.sub.9                             H         H        Cl       n-C.sub.5 H.sub.11                                H         H        Cl       sec-C.sub.5 H.sub.11                              H         H        Cl       n-C.sub.6 H.sub.13                                H         H        Cl       n-C.sub.7 H.sub.15                                H         H        Cl       sec.-C.sub.7 H.sub.15                             H         H        Cl       Ethoxy                                            H         H        Cl       Propoxy                                           H         H        Cl       1-Methylethoxy                                    H         H        Cl       n-Butoxy                                          H         H        Cl       1-Methylpropoxy                                   H         H        Cl       2-Methylpropoxy                                   H         H        Cl       1,1-Dimethylethoxy                                H         H        Cl       n-Pentyloxy                                       H         H        Cl       n-Hexyloxy                                        H         H        Cl       Cyclopentyl                                       H         H        Cl       Cyclopentenyl                                     H         H        Cl       Cyclohexyl                                        H         H        Cl       Phenyl                                            H         H        CH.sub.3 i-C.sub.3 H.sub.7                                 H         H        CH.sub.3 n-C.sub.3 H.sub.7                                 H         H        CH.sub.3 n-C.sub.4 H.sub.9                                 H         H        CH.sub.3 sec.-C.sub.4 H.sub.9                              H         H        CH.sub.3 i-C.sub.4 H.sub.9                                 H         H        CH.sub.3 tert.-C.sub.4 H.sub.9                             H         H        CH.sub.3 n-C.sub.5 H.sub.11                                H         H        CH.sub.3 sec-C.sub.5 H.sub.11                              H         H        CH.sub.3 n-C.sub.6 H.sub.13                                H         H        CH.sub.3 n-C.sub.7 H.sub.15                                H         H        CH.sub.3 sec.-C.sub.7 H.sub.15                             H         H        CH.sub.3 Ethoxy                                            H         H        CH.sub.3 Propoxy                                           H         H        CH.sub.3 1-Methylethoxy                                    H         H        CH.sub.3 n-Butoxy                                          H         H        CH.sub.3 1-Methylpropoxy                                   H         H        CH.sub.3 2-Methylpropoxy                                   H         H        CH.sub.3 1,1-Dimethylethoxy                                H         H        CH.sub.3 n-Pentyloxy                                       H         H        CH.sub.3 n-Hexyloxy                                        H         H        CH.sub.3 Cyclopentyl                                       H         H        CH.sub.3 Cyclopentenyl                                     H         H        CH.sub.3 Cyclohexyl                                        H         H        CH.sub.3 Phenyl                                            CH.sub.3  H        CH.sub.3 i-C.sub.3 H.sub.7                                 CH.sub.3  H        CH.sub.3 n-C.sub.3 H.sub.7                                 CH.sub.3  H        CH.sub.3 n-C.sub.4 H.sub.9                                 CH.sub.3  H        CH.sub.3 sec.-C.sub.4 H.sub.9                              CH.sub.3  H        CH.sub.3 i-C.sub.4 H.sub.9                                 CH.sub.3  H        CH.sub.3 tert.-C.sub.4 H.sub.9                             CH.sub.3  H        CH.sub.3 n-C.sub.5 H.sub.11                                CH.sub.3  H        CH.sub.3 sec-C.sub.5 H.sub.11                              CH.sub.3  H        CH.sub.3 n-C.sub.6 H.sub.13                                CH.sub.3  H        CH.sub.3 n-C.sub.7 H.sub.15                                CH.sub.3  H        CH.sub.3 sec.-C.sub.7 H.sub.15                             CH.sub.3  H        CH.sub.3 Ethoxy                                            CH.sub.3  H        CH.sub.3 Propoxy                                           CH.sub.3  H        CH.sub.3 1-Methylethoxy                                    CH.sub.3  H        CH.sub.3 n-Butoxy                                          CH.sub.3  H        CH.sub.3 1-Methylpropoxy                                   CH.sub.3  H        CH.sub.3 2-Methylpropoxy                                   CH.sub.3  H        CH.sub.3 1,1-Dimethylethoxy                                CH.sub.3  H        CH.sub.3 n-Pentyloxy                                       CH.sub.3  H        CH.sub.3 n-Hexyloxy                                        CH.sub.3  H        CH.sub.3 Cyclopentyl                                       CH.sub.3  H        CH.sub.3 Cyclopentenyl                                     CH.sub.3  H        CH.sub.3 Cyclohexyl                                        CH.sub.3  H        CH.sub.3 Phenyl                                            ______________________________________                                    

                  TABLE D                                                         ______________________________________                                         ##STR10##                     I.4                                            R.sup.3        R                                                              ______________________________________                                        CF.sub.3       i-C.sub.3 H.sub.7                                              CF.sub.3       n-C.sub.3 H.sub.7                                              CF.sub.3       n-C.sub.4 H.sub.9                                              CF.sub.3       sec.-C.sub.4 H.sub.9                                           CF.sub.3       i-C.sub.4 H.sub.9                                              CF.sub.3       tert.-C.sub.4 H.sub.9                                          CF.sub.3       n-C.sub.5 H.sub.11                                             CF.sub.3       sec.-C.sub.5 H.sub.11                                          CF.sub.3       n-C.sub.6 H.sub.13                                             CF.sub.3       n-C.sub.7 H.sub.15                                             CF.sub.3       sec.-C.sub.7 H.sub.15                                          CF.sub.3       1-Methylvinyl                                                  CF.sub.3       2-Methylvinyl                                                  CF.sub.3       Allyl                                                          CF.sub.3       2-Methylallyl                                                  CF.sub.3       2-Ethylallyl                                                   CF.sub.3       1-Methylallyl                                                  CF.sub.3       l-Ethylallyl                                                   CF.sub.3       1-Methyl-2-butenyl                                             CF.sub.3       l-Ethyl-2-butenyl                                              CF.sub.3       1-Isopropyl-2-butenyl                                          CF.sub.3       1-n-Butyl-2-butenyl                                            CF.sub.3       1-Methyl-2-pentenyl                                            CF.sub.3       1,4-Dimethyl-2-pentenyl                                        CF.sub.3       Propargyl                                                      CF.sub.3       2-Butynyl                                                      CF.sub.3       3-Butynyl                                                      CF.sub.3       Ethoxy                                                         CF.sub.3       Propoxy                                                        CF.sub.3       1-Methylethoxy                                                 CF.sub.3       n-Butoxy                                                       CF.sub.3       1-Methylpropoxy                                                CF.sub.3       2-Methylpropoxy                                                CF.sub.3       1,1-Dimethylethoxy                                             CF.sub.3       n-Pentyloxy                                                    CF.sub.3       n-Hexyloxy                                                     CF.sub.3       2-Ethylhexyloxy                                                CF.sub.3       2-Propenyloxy                                                  CF.sub.3       2-Butenyloxy                                                   CF.sub.3       2-Methyl-2-propenyloxy                                         CF.sub.3       2-Pentenyloxy                                                  CF.sub.3       3-Pentenyloxy                                                  CF.sub.3       3-Chloro-2-propenyloxy                                         CF.sub.3       2,3-Dichloro-2-propenyloxy                                     CF.sub.3       2,3,3-Trichloropropenyloxy                                     CF.sub.3       2-Propynyloxy                                                  CF.sub.3       2-Butynyl-oxy                                                  CF.sub.3       3-Butynyl-oxy                                                  CF.sub.3       1-Methyl-2-propynyloxy                                         CF.sub.3       Cyclopropyl                                                    CF.sub.3       Cyclobutyl                                                     CF.sub.3       Cyclopentyl                                                    CF.sub.3       Cyclohexyl                                                     CF.sub.3       3-Cyclopentenyl                                                CF.sub.3       1-Cyclopentenyl                                                CF.sub.3       3-Cyclohexenyl                                                 CF.sub.3       1-Cyclohexenyl                                                 CF.sub.3       Cyclopentyloxy                                                 CF.sub.3       Cyclohexyloxy                                                  CF.sub.3       3-Cyclopentenyloxy                                             CF.sub.3       3-Cyclohexenyloxy                                              CH.sub.3       i-C.sub.3 H.sub.7                                              CH.sub.3       n-C.sub.3 H.sub.7                                              CH.sub.3       n-C.sub.4 H.sub.9                                              CH.sub.3       sec.-C.sub.4 H.sub.9                                           CH.sub.3       i-C.sub.4 H.sub.9                                              CH.sub.3       tert.-C.sub.4 H.sub.9                                          CH.sub.3       n-C.sub.5 H.sub.11                                             CH.sub.3       sec.-C.sub.5 H.sub.11                                          CH.sub.3       n-C.sub.6 H.sub.13                                             CH.sub. 3      n-C.sub.7 H.sub.15                                             CH.sub.3       sec.-C.sub.7 H.sub.15                                          CH.sub.3       Ethoxy                                                         CH.sub.3       Propoxy                                                        CH.sub.3       1-Methylethoxy                                                 CH.sub.3       n-Butoxy                                                       CH.sub.3       1-Methylpropoxy                                                CH.sub.3       2-Methylpropoxy                                                CH.sub.3       1,1-Dimethylethoxy                                             CH.sub.3       n-Pentyloxy                                                    CH.sub.3       n-Hexyloxy                                                     CH.sub.3       Cyclopentyl                                                    CH.sub.3       Cyclopentenyl                                                  CH.sub.3       Cyclohexyl                                                     CH.sub.3       1-Ethylpropoxy                                                 CH.sub.3       Cyclopentyloxy                                                 CH.sub.3       3-Cyclohexenyloxy                                              CH.sub.3       2-Methyl-2-propenyloxy                                         CHF.sub.2      Phenyl                                                         CHF.sub.2      2-Fluorophenyl                                                 ______________________________________                                    

                  TABLE E                                                         ______________________________________                                         ##STR11##                     I.5                                            R.sup.3        R                                                              ______________________________________                                        CF.sub.3       i-C.sub.3 H.sub.7                                              CF.sub.3       n-C.sub.3 H.sub.7                                              CF.sub.3       n-C.sub.4 H.sub.9                                              CF.sub.3       sec.-C.sub.4 H.sub.9                                           CF.sub.3       i-C.sub.4 H.sub.9                                              CF.sub.3       tert.-C.sub.4 H.sub.9                                          CF.sub.3       n-C.sub.5 H.sub.11                                             CF.sub.3       sec.-C.sub.5 H.sub.11                                          CF.sub.3       n-C.sub.6 H.sub.13                                             CF.sub.3       n-C.sub.7 H.sub.15                                             CF.sub.3       sec.-C.sub.7 H.sub.15                                          CF.sub.3       1-Methylvinyl                                                  CF.sub.3       2-Methylvinyl                                                  CF.sub.3       Allyl                                                          CF.sub.3       2-Methylallyl                                                  CF.sub.3       2-Ethylallyl                                                   CF.sub.3       1-Methylallyl                                                  CF.sub.3       l-Ethylallyl                                                   CF.sub.3       1-Methyl-2-butenyl                                             CF.sub.3       l-Ethyl-2-butenyl                                              CF.sub.3       1-Isopropyl-2-butenyl                                          CF.sub.3       1-n-Butyl-2-butenyl                                            CF.sub.3       1-Methyl-2-pentenyl                                            CF.sub.3       1,4-Dimethyl-2-pentenyl                                        CF.sub.3       Propargyl                                                      CF.sub.3       2-Butynyl                                                      CF.sub.3       3-Butynyl                                                      CF.sub.3       Ethoxy                                                         CF.sub.3       Propoxy                                                        CF.sub.3       1-Methylethoxy                                                 CF.sub.3       n-Butoxy                                                       CF.sub.3       1-Methylpropoxy                                                CF.sub.3       2-Methylpropoxy                                                CF.sub.3       1,1-Dimethylethoxy                                             CF.sub.3       n-Pentyloxy                                                    CF.sub.3       n-Hexyloxy                                                     CF.sub.3       2-Ethylhexyloxy                                                CF.sub.3       2-Propenyloxy                                                  CF.sub.3       2-Butenyloxy                                                   CF.sub.3       2-Methyl-2-propenyloxy                                         CF.sub.3       2-Pentenyloxy                                                  CF.sub.3       3-Pentenyloxy                                                  CF.sub.3       3-Chloro-2-propenyloxy                                         CF.sub.3       2,3-Dichloro-2-propenyloxy                                     CF.sub.3       2,3,3-Trichloropropenyloxy                                     CF.sub.3       2-Propynyloxy                                                  CF.sub.3       2-Butynyl-oxy                                                  CF.sub.3       3-Butynyl-oxy                                                  CF.sub.3       1-Methyl-2-propynyloxy                                         CF.sub.3       Cyclopropyl                                                    CF.sub.3       Cyclobutyl                                                     CF.sub.3       3-Cyclopentenyl                                                CF.sub.3       1-Cyclopentenyl                                                CF.sub.3       3-Cyclohexenyl                                                 CF.sub.3       Cyclopentyloxy                                                 CF.sub.3       3-Cyclopentenyloxy                                             CF.sub.3       3-Cyclohexenyloxy                                              CH.sub.3       i-C.sub.3 H.sub.7                                              CH.sub.3       n-C.sub.3 H.sub.7                                              CH.sub.3       n-C.sub.4 H.sub.9                                              CH.sub.3       sec.-C.sub.4 H.sub.9                                           CH.sub.3       i-C.sub.4 H.sub.9                                              CH.sub.3       tert.-C.sub.4 H.sub.9                                          CH.sub.3       n-C.sub.5 H.sub.11                                             CH.sub.3       sec.-C.sub.5 H.sub.11                                          CH.sub.3       n-C.sub.6 H.sub.13                                             CH.sub.3       n-C.sub.7 H.sub.15                                             CH.sub.3       sec.-C.sub.7 H.sub.15                                          CH.sub.3       Ethoxy                                                         CH.sub.3       Propoxy                                                        CH.sub. 3      1-Methylethoxy                                                 CH.sub.3       n-Butoxy                                                       CH.sub.3       1-Methylpropoxy                                                CH.sub.3       2-Methylpropoxy                                                CH.sub.3       1,1-Dimethylethoxy                                             CH.sub.3       n-Pentyloxy                                                    CH.sub.3       n-Hexyloxy                                                     CH.sub.3       Cyclopentenyl                                                  CH.sub.3       1-Ethyl-propoxy                                                CH.sub.3       Cyclopentyloxy                                                 CH.sub.3       2-Cyclohexenyloxy                                              CH.sub.3       2-Methyl-2-propenyloxy                                         CHF.sub.2      i-C.sub.3 H.sub.7                                              CHF.sub.2      n-C.sub.3 H.sub.7                                              CHF.sub.2      n-C.sub.4 H.sub.9                                              CHF.sub.2      sec.-C.sub.4 H.sub.9                                           CHF.sub.2      i-C.sub.4 H.sub.9                                              CHF.sub.2      tert.-C.sub.4 H.sub.9                                          CHF.sub.2      n-C.sub.5 H.sub.11                                             CHF.sub.2      sec.-C.sub.5 H.sub.11                                          CHF.sub.2      n-C.sub.6 H.sub.13                                             CHF.sub.2      n-C.sub.7 H.sub.15                                             CHF.sub.2      sec.-C.sub.7 H.sub.15                                          CHF.sub.2      Ethoxy                                                         CHF.sub.2      Propoxy                                                        CHF.sub.2      1-Methylethoxy                                                 CHF.sub.2      n-Butoxy                                                       CHF.sub.2      1-Methylpropoxy                                                CHF.sub.2      2-Methylpropoxy                                                CHF.sub.2      1,1-Dimethylethoxy                                             CHF.sub.2      n-Pentyloxy                                                    CHF.sub.2      n-Hexyloxy                                                     CHF.sub.2      Cyclopentenyl                                                  CHF.sub.2      Cyclohexyl                                                     CHF.sub.2      1-Ethyl-propoxy                                                CHF.sub.2      Cyclopentyloxy                                                 CHF.sub.2      2-Cyclohexenyloxy                                              CHF.sub.2      2-Methyl-2-propenyloxy                                         CHF.sub.2      Phenyl                                                         CF.sub.3       2-Fluorophenyl                                                 CH.sub.3       Phenyl                                                         CH.sub.3       2-Fluorophenyl                                                 CHF.sub.2      Phenyl                                                         CHF.sub.2      2-Fluorophenyl                                                 ______________________________________                                    

The novel active ingredients are particularly suitable for protectingvarious materials against degradation or destruction by bacteria orfungi or from being attacked by and covered with microorganisms.Examples of materials which can be preserved or microbicidally finishedwith the novel active ingredients are glues and adhesives, starchsolutions, wax emulsions, clay emulsions, sizes, finishes, spinningbaths, gelatine formulations, putty, joint sealants, cooling lubricants,drilling oils, fuels, plastic dispersions, emulsion paints, textiles,leather, raw hides and cosmetics. The compounds are also suitable asanti-slime agents in the paper industry, in cooling towers and in airmoistening units.

The compounds I are also suitable for protecting the following plantspecies against attack by microorganisms:

cereals (e.g., wheat, barley, rye, oats, rice, sorghum and relatedspecies); beets (e.g., sugar and fodder beets); pomes, drupes andaggregate fruit (e.g., apples, pears, plums, peaches, almonds, cherries,strawberries, raspberries and blackberries); legumes (e.g., beans,lentils, peas, soybeans); oil-yielding crops (e.g., rape, mustard,poppies, olives, sunflowers, coconuts, castor-oil beans, cocoa beans,groundnuts); cucurbits (e.g., pumpkins, cucumbers, melons);fiber-yielding plants (e.g., cotton, flax, hemp, jute); citrus fruit(e.g., oranges, lemons, grapefruit, tangerines); vegetables (e.g.,spinach, lettuce, asparagus, cabbage varieties, carrots, onions,tomatoes, potatoes, paprika); laurel species (e.g., avocado, cinnamomum,camphor) or plants such as Indian corn, tobacco, nuts, coffee, sugarcane, tea, grapes, hops, and banana and rubber trees. For the purposesof the present invention, the term "plants" is also taken to mean alltypes of other green growth, whether ornamentals, grassy areas,embankments, or generally low-growing cover crops.

For example the following microorganisms may be combatted with the novelcompounds I:

Straphylococcus aureus, Escherichia coli, Klebsielle pneumoniae,Citrobacter freundii, Proteus vulgaris, Pseudomonas aeruginosa,Desulfovibrio desulfuricans, Streptoverticillium rubrireticuli,Aspergillus niger, Aspergillus versicolor, Penicillium funiculosum,Penicillium expansum, Penicillium glaucum, Paecilomyces variotii,Trichoderma viride, Chaetomium globosum, Aspergillus amstelodami, Phomapigmentovora, Phoma violacea, Aureobasidium pullulans, Saccharomycescerevisiae, Alternaria tenuis, Stemphylium macrosporoideum, Cladosporiumherbarum, Cladosporium resinae, Candida albicans, Trichophytonmentagrophytes, Geotrichum candidans, Monilia sitophila, Scenedesmusquadricauda, Chlorella vulgaris, Nostoc muscorium, Oscillatoria limosaand Anabaena constricta.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

The fungicides generally contain from 0.1 to 95, and preferably from 0.5to 90, wt % of active ingredient. The active ingredients are used in apurity of from 90 to 100, and preferably from 95 to 100, % (according tothe NMR/HPLC/GC spectrum).

Usual application concentrations are--based on the weight of thematerial to be protected--from 0.001 to 5, and preferably from 0.01 to2, wt % of active ingredient; when the active ingredients are used fortreating water, in oil production, in drilling and cutting oils, fuels,in swimming baths, cooling towers, air moistening units or in the paperindustry, amounts of from 5 to 500 ppm are sufficient. Ready-to-usedisinfectant solutions contain for instance from 0.5 to 10 wt % ofactive ingredient.

Examples of such formulations are given below:

I. A solution of 90 parts by weight of compound no. 7 and 10 parts byweight of N-methyl-α-pyrrolidone, which is suitable for application inthe form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 2, 80 parts byweight of xylene, 10 parts by weight of the adduct of 8 to 10 moles ofethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonic acid, and 5 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil. By finely dispersing the mixture in 100,000 parts by weightof water, an aqueous dispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 4, 40parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil. A mixture of this dispersion with 100,000 parts by weightof water contains 0.02 wt % of the active ingredient.

IV. An aqueous dispersion of 20 parts by weight of compound no. 3, 25parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction having a boiling point between 210° and 280° C., and 10 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil. The mixture of this dispersion with 100,000 parts by weightof water contains 0.02 wt % of the active ingredient.

V. A hammer-milled mixture of 80 parts by weight of compound no. 1, 3parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 10 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 7 parts by weight of powderedsilica gel. By finely dispersing the mixture in 20,000 parts by weightof water, a spray liquor containing 0.1 wt % of the active ingredient isobtained.

VI. An intimate mixture of 3 parts by weight of compound no. 5 and 97parts by weight of particulate kaolin. The dust contains 3 wt % of theactive ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 6, 92parts by weight of powdered silica gel and 8 parts by weight of paraffinoil sprayed onto the surface of this silica gel. This formulation of theactive ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no.4, 10 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 5, 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil.

X. A hammer-milled mixture of 10 parts by weight of compound no. 1, 4parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonicacid, 20 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, 38 parts by weight of silica gel,and 38 parts by weight of kaolin. By finely dispersing the mixture in10,000 parts by weight of water, a spray liquor containing 0.1 wt % ofthe active ingredient is obtained.

Used alone, the active ingredients act as low-foaming biocides. Asignificant increase in the action of biocidal formulations containingthese compounds is achieved if tri-C₆ - to C₁₂ -alkylmethylammoniumsalts, preferably in amounts of from 20 to 40 wt %, based on the weightof compounds of the general formula I, are added.

The active ingredients may also be mixed with other, prior art,microbicides. In many instances, a synergistic effect is achieved, i.e.,the microbicidal action of the mixture is greater than the added actionsof its individual components.

Prior art microbicides may be added to the novel substances in a weightratio of from 1:100 to 100:1.

Examples of such active ingredients are as follows:

2-(thiocyanomethylthio)-benzothiazole

1-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-1H-imidazole

2,4,5,6-tetrachloroisophthalodinitrile

methylene bisthiocyanate

tributyltin oxide, naphthenate, benzoate, salicylate

mercaptobenzothiazole

1,2-benzisothiazolone and its alkali metal salts

alkali metal compounds of N'-hydroxy-N-cyclohexyldiazenium oxide

2-(methoxycarbonylamino)-benzimidazole

2-methyl-3-oxo-5-chlorothiazolin-3-one

trihydroxymethylnitromethane

glutardialdehyde

chloroacetamide

polyhexamethylene bisguanide

5-chloro-2-methyl-4-isothiazolin-3-one+magnesium salts

3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione

hexahydrotriazine

N,N-methylolchloroacetamide

2-n-octyl-4-isothiazolin-3-one

oxazolidines

bisoxazolidines

2,5-dihydro-2,5-dialkoxy-2,5-dialkylfurans

diethyldodecylbenzylammonium chloride

dimethyloctadecyldimethylbenzylammonium chloride

dimethyldidecylammonium chloride

dimethyldidodecylammonium chloride

trimethyltetradecylammonium chloride

benzyldimethylalkyl-(C₁₂ -C₁₈)-ammonium chloride

dichlorobenzyldimethyldodecylammonium chloride

cetylpyridinium chloride

cetylpyridinium bromide

cetyltrimethylammonium chloride

laurylpyridinium chloride

laurylpyridinium bisulfate

benzyldodecyldi(beta-oxyethyl)-ammonium chloride

dodecylbenzyltrimethylammonium chloride

n-alkyldimethylbenzylammonium chloride

(alkyl radical: 40% C₁₂, 50% C₁₄, 10% C₁₆)

lauryldimethylethylammonium ethyl sulfate

n-alkyldimethyl-(1-naphthylmethyl)-ammonium chloride

(alkyl radical: 98% C₁₂, 2% C₁₄)

cetyldimethylbenzylammonium chloride

lauryldimethylbenzylammonium chloride

Examples of further compounds which may be admixed are:

1,3-dimethylol-5,5-dimethylhydantoin

dimethylolurea

tetramethylolacetylenediurea

dimethylolglyoxalmonoureine

hexamethylenetetramine

glyoxal

glutardialdehyde

N-methylolchloroacetamide

1-(hydroxymethyl)-5,5-dimethylhydantoin

1,3-bis-(hydroxymethyl)-5,5-dimethylhydantoin

imidazolidinylurea

1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantan chloride

1,3-bis-(β-ethylhexyl)-5-methyl-5-amino-hexahydropyrimidine

1,3,5-tris-(hydroxyethyl)-1,3,5-hexahydrotriazine

1,2-dibromo-2,4-dicyanobutane

5-bromo-5-nitro-1,3-dioxane

2-bromo-2-nitropropanediol

1,1'-hexamethylene-bis-[5-(4-chlorophenyl)-biguanide]

4,4-diaminodiphenoxypropane

2-bromo-2-nitropropane-1,3-diol

sorbic acid and its salts

p-hydroxybenzoic acid and its esters and salts

zinc-2-pyridinethiol-N-oxide

2-[(hydroxylmethyl)amino]-ethanol

dithio-2,2'-bis(benzmethylamide)

5-chloro-2-(2,4-dichlorophenoxy)-phenol

thio-bis-(4-chlorophenol)

o-phenylphenol

chloromethyl-diiodomethylsulfone

p-chlorophenyl-3-iodopropargylformal.

SYNTHESIS EXAMPLES

The directions given in the synthesis examples below were used, afterappropriate modification of the starting materials, to obtain furthercompounds I. The compounds thus obtained are listed in the tables belowwith their physical data.

1.N-(2-(1-Methylethyl)phenyl)-1-methyl-3-trifluoromethylpyrazole-4-carboxamide##STR12##

a) Ethyl 1-methyl-3-trifluoromethylpyrazole-4-carboxylate

At -35° to -40° C., 7.20 g of ethyl ethoxymethyl-4,4,4-trifluoroacetateis dripped into a solution of 1.38 g of methylhydrazine in 30 ml ofethanol, and the mixture is stirred for 1 hour at 0° C. and for 1 hourat 40° C. After evaporation of the solvent there is isolated 6.02 g ofcrystals of melting point 52°-54° C., which consisted to the extent of85% of the above ester and 15% of ethyl1-methyl-5-trifluoromethylpyrazole-4-carboxylate.

b) 1-Methyl-3-trifluoromethylpyrazole-4-carboxylic acid

41.5 g of the above crude product from a) is introduced into 7.4 g ofsodium hydroxide in 187 ml of water, 3 ml of ethanol is added and themixture is stirred for 12 hours at room temperature. The small amount ofresidue is filtered off, and the filtrate is acidified with concentratedhydrochloric acid to a pH of 3. After the product has been suctionfiltered, washed with cold water and dried, there is isolated 29.0 g ofthe above acid of m.p. 201°-202° C.

c) 1-Methyl-3-trifluoromethylpyrazol-4-carboxylicacid-2'-sec.-butylanilide

At 0° C., 1.90 g of thionyl chloride is dripped into a solution of 2.91g of the acid from b) and 1.60 g of triethylamine in 30 ml ofdichloromethane, and the mixture is stirred for 3 hours at 0° C. At thesame temperature, a mixture of 2.43 g of 2-sec.-butylaniline and 1.60 gof triethylamine is then dripped in and the mixture is stirred for 12hours at room temperature. After the batch has been washed with 60 ml ofwater and dried, and the solvent has been evaporated, there is isolated4.30 g of crude product from which recrystallization with cyclohexanegives 3.50 g of the above anilide of m.p. 126°-129° C.

EXAMPLE 2

At 0° C., 2.4 g of triethylamine is added to a solution of 3.25 g of3-chlorothiophene-2-carboxylic acid in 40 ml of dichloromethane, 2.62 gof thionyl chloride is added at 0° C., and the mixture is stirred for 16hours at room temperature. After cooling to 0° C., a mixture of 3.28 gof 2-isobutylaniline and 2.4 g of triethylamine is dripped in and theresultant mixture is stirred for 12 hours at room temperature. After thebatch has been washed with 50 ml of 8% strength sulfuric acid, 30 ml ofwater, 30 ml of 10% strength sodium bicarbonate solution and 30 ml ofwater, there is obtained 4.6 g of an oil which, after purification bycolumn chromatography over silica gel using a 99:1 mixture ofcyclohexane and ethyl acetate, gives 3.6 g of3-chlorothiophene-2-carboxylic acid-2-isobutylaniline as an oil.

EXAMPLE 3

a) At 0° C., 2.5 g of 2-chloro-4-trifluoromethyl-5-thiazolecarboxylicchloride (J. Het. Chem. 22, 1621 (1985)) is dripped into a solution of1.5 g of 2-isobutylaniline and 1.0 g of triethylamine in 12 ml oftetrahydrofuran. After the reaction mixture has been stirred for 12hours at room temperature, it is diluted with 250 ml of water andextracted twice, each time with 70 ml of ethyl acetate. After drying,filtering and evaporating off the solvent, and after the crude producthas been made into a paste with diisopropyl ether, there is isolated 2.8g of 2-chloro-4-trifluoromethyl-5-thiazolecarboxylicacid-2'-isobutylanilide of m.p. 107°-108° C.

b) 30 ml of ammonia is pressured into a solution of 9.0 g of the aboveproduct and 0.7 g of phenol-4-sulfonic acid (65% strength) in 100 ml ofethanol in an autoclave, and the mixture is stirred at 120° C. for 24hours. After the pressure has been released, the charge is filtered andevaporated down, and the crude product is partitioned between 300 ml ofethyl acetate and 100 ml of water. After drying and evaporation of thesolvent, there is isolated from the organic phase 7.0 g of2-amino-4-trifluoromethyl-5-thiazolecarboxylic acid-2'-isobutylanilideof m.p. 193-196.

                  TABLE 1                                                         ______________________________________                                         ##STR13##                     I                                                                                  Phys.                                                                         data                                      Ex.                                 [m.p.                                     no.  R             A                (°C.)]                             ______________________________________                                         1   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               Al               106-107                                    2   CH.sub.2 CH(CH.sub.3).sub.2                                                                 Al               105-108                                    3   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               3-Cl-thien-2-yl  oil                                        4   CH.sub.2 CH(CH.sub.3).sub.2                                                                 3-Cl-thien-2-yl  oil                                        5   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               2-NH.sub.2 -4-CF.sub.3 -thiazol-5-yl                                                           189-195                                    6   CH.sub.2 CH(CH.sub.3).sub.2                                                                 2-NH.sub.2 -4-CF.sub.3 -thiazol-5-yl                                                           193-196                                    7   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               1-CH.sub.3 -3-CF.sub.3 -pyrazol-4-yl                                                           126-129                                    8   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               2-NH.sub.2, 4-CH.sub.3 -thiazol-5-yl                                                           229-232                                    9   CH.sub.2 CH(CH.sub.3).sub.2                                                                 2-NH.sub.2, 4-CH.sub.3 -thiazol-5-yl                                                           219-220                                   10   Cyclopentyl   2-NH.sub.2, 4-CH.sub.3 -thiazol-5-yl                                                           256-257                                   11   Cyclohexy     2-NH.sub.2, 4-CH.sub.3 -thiazol-5-yl                                                           300-301                                   12   Phenyl        2-NH.sub.2, 4-CH.sub.3 -thiazol-5-yl                                                           277-278                                   13   Cyclopentyl   2-NH.sub.2, 4-CF.sub.3 -thiazol-5-yl                                                           208-209                                   14   Cyclohexyl    2-NH.sub.2, 4-CF.sub.3 -thiazol-5-yl                                                           242-246                                   15   Phenyl        2-NH.sub.2, 4-CF.sub.3 -thiazol-5-yl                                                           214-217                                   16   CH.sub.2 CH(CH.sub.3).sub.2                                                                 1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           137-139                                   17   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               1,3-(CH.sub.3).sub.3 -pyrazol-4-yl                                                             158-160                                   18   CH.sub.2 CH(CH.sub.3).sub.2                                                                 1,3-(CH.sub.3).sub.3 -pyrazol-4-yl                                                             121-123                                   19   OCF.sub.2 CHF.sub.2                                                                         1,3-(CH.sub.3).sub.3 -pyrazol-4-yl                                                             114-115                                   20   CH.sub.2 CH(CH.sub.2 CH.sub.3).sub.2                                                        1,3-(CH.sub.3).sub.3 -pyrazol-4-yl                                                             91-93                                     21   Cyclopentyl   Al               130-133                                   22   Cyclohexyl    Al               126-128                                   23   Phenyl        Al               93-94                                     24   Cyclopentyl   3-Cl-thien-2-yl  oil                                       25   Cyclopent-2-en-1-yl                                                                         3-Cl-thien-2-yl  oil                                       26   Cyclohexyl    3-Cl-thien-2-yl  oil                                       27   Phenyl        3-Cl-thien-2-yl  96-99                                     28   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               3-CH.sub.3 -thien-2-yl                                                                         oil                                       29   CH.sub.2 CH(CH.sub.3).sub.2                                                                 3-CH.sub.3 -thien-2-yl                                                                         78-80                                     30   Cyclopentyl   3-CH.sub.3 -thien-2-yl                                                                         oil                                       31   Cyclohexyl    3-CH.sub.3 -thien-2-yl                                                                         95-97                                     32   Phenyl        3-CH.sub.3 -thien-2-yl                                                                         oil                                       33   CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               1-CH.sub.3, 3-CHF.sub.2 -pyrazol-4-yl                                                           97-100                                   34   CH.sub.2 CH(CH.sub.3).sub.2                                                                 1-CH.sub.3, 3-CHF.sub.2 -pyrazol-4-yl                                                          122-126                                   35   Phenyl        1-CH.sub.3, 3-CHF.sub.2 -pyrazol-4-yl                                                          115-118                                   36   Phenyl        1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           147-148                                   37   4-Cl-phenyl   1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           151-153                                   38   4-OCH.sub.3 -phenyl                                                                         1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           152-154                                   39   4-F-phenyl    1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           156-157                                   40   3-Cl-phenyl   1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           92-94                                     41   2-CH.sub.3 -phenyl                                                                          1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           119-122                                   42   CH.sub.2 CH(C.sub.2 H.sub.5).sub.2                                                          1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           83-85                                     43   OCF.sub.2 CHF.sub.2                                                                         1-CH.sub.3, 3-CF.sub.3 -pyrazol-4-yl                                                           96-98                                     44   Phenyl        1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             158-160                                   45   4-Cl-phenyl   1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             165-166                                   46   4-OCH.sub.3 -phenyl                                                                         1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             156-157                                   47   4-F-phenyl    1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             175-176                                   48   3-Cl-phenyl   1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             104-106                                   49   2-CH.sub.3 -phenyl                                                                          1,3-(CH.sub.3).sub.2 -pyrazol-4-yl                                                             137-139                                   ______________________________________                                    

Examples illustrating the biological action:

Use Example

Action on Botrytis cinerea in paprika

Paprika seedlings of the "Neusiedler Ideal Elite" variety were sprayed,after 4 to 5 leaves were well developed, to runoff with aqueoussuspensions containing (dry basis) 80% of active ingredient and 20% ofemulsifier. After the sprayed-on layer had dried, the plants weresprinkled with a conidial suspension of the fungus Botrytis cinerea, andplaced for 5 days at 22° to 24° C. in a chamber of high humidity.

After this time, the untreated control plants exhibited 80% fungusattack, whereas the plants treated with 500 ppm of compounds nos. 2, 5,7, 8, 9, 12, 13, 14, 15, 17, 18, 19 and 20 exhibited 15% attack at most.

We claim:
 1. A carboxanilide of the formula I ##STR14## where thesubstituents have the following meanings: R is C₃ -C₁₂ -alkyl, C₂ -C₁₂-alkoxy, C₃ -C₁₂ -alkenyl, C₄ -C₁₂ -alkenyloxy, C₄ -C₆ -alkynyl, C₃ -C₆-alkynyloxy, where these groups can be partially or completelyhalogenated; phenyl, which can carry one to five halogens and/or one tothree of the following radicals: C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -alkylthio or C₁ -C₄-haloalkylthio;R¹ is C₁ -C₄ -alkyl or C₁ -C₄ -haloalkyl.
 2. Acarboxanilide of the formula I as defined in claim 1, where R has themeanings given in claim 1 and R¹ is methyl or C₁ -haloalkyl.
 3. Acarboxanilide of the formula I as defined in claim 1, where R has themeanings given in claim 1 and R¹ is methyl, difluoromethyl ortrifluoromethyl.
 4. An agent for combatting harmful fungi and containinga fungicidal amount of a compound of the formula I as defined in claim1, and inert additives.
 5. A process for combatting harmful fungi,wherein the fungi, their habitat and/or the plants or materials to bekept free from the fungi are treated with a fungicidally effectiveamount of a compound of the formula I as defined in claim
 1. 6. Theprocess of claim 5, wherein the fungus combatted is Botrytis.